Spinning solution and a process of making it



Patented Apr. 20, 1948 SPINNING. SOLUTION MAKIN William 0. Israel,Lakewood, Ohio,

AND A PROCESS G I'I" Minor to Industrial Rayon Corporation, Cleveland,Ohio, a corporation oi Delaware No Drawing. Application July 12, 1943,

Serial No. 494,395

18 Claims. 1

The present-invention relates to the production of viscose rayon ofdiminished luster and it provides a new and improved viscose spinningsolution for use in the production of such rayon as well as a process bywhich this spinning solution may be produced.

It, has heretofore been the practice to produce viscose rayon oi dullluster by one of several different methods. According to one method,apigment, such as titanium dioxide, is incorporated in the spinningsolution; This method is fairly effective in producing yarns of reducedluster, but for yarn of very low luster, the quantity of pigmentrequired is such that the yarn is weakened appreciably and the solutionhas an abrasive action on the spinning orifice. In addition, as is wellknown, yarns delustered by pigments regain their luster upon being dyedto a dark color since the pigment has little efiect upon the smoothnessof the filament surface.

According to another method, it has been proposed to incorporate variousoils and fats in viscose spinning solutions. Refined mineral oil forexample may be used as the delusterant. However, such oil dispersions inviscose tend to agglomerate and produce breaks or weak spots in thefilament. Pine oil may be used to overcome this disadvantage but itdelusters only partially and, furthermore, it has a persistent residualodor which is difiicult to remove. Both mineral and pine oil impart aslightly yellowish cast to rayon.

Now, in accordance with the-present invention, it has been found thatthe above-mentioned difficulties may be obviated and that viscose rayonof diminished luster may be produced by incorporating in a viscosespinning solution, a, delusterant and as a dispersing agent therefor, asuitable amount of a reaction product of an alkylene oxide and anunsaturated or hydroxy terpene, or mixtures of such terpenes, which hasbeen produced by the reaction of at least three moles of the alkyleneoxide per mole of the terpene.

The terpene derivatives which are employed as dispersing agents inaccordance with the present invention and a method by which they may beproduced are described in my copending application Serial No. 494,394,filed on July 12, 1943 (now Patent No. 2,440,093), for Terpenederivatives and method of producing the same." In general,

the method by which these terpene derivatives.

are produced comprises admixing a suitable amount of an alkalinecatalyst with an unsaturated terpene, a hydroxy terpene, or mixturethereof, and placing the mixture in an autoclave which is then heated toa temperature of about 125 C. to about 150 C. to initiate the reaction,and gradually introducing into the autoclave, a

suitable amount of an alkylene oxide to form a reaction product in whichat least three moles of alkylene oxide per mole of terpene are reacted.The compounds having from three to seven moles of alkylene oxide permole of terpene provide optimum water-dispersability oi the delusterantsin the viscose.

Upon completion of the above-mentioned reaction, or prior thereto, asindicated by a drop to atmospheric pressure, and by a rapid decrease intemperature, the introduction of the alkylene oxide into the terpene,hydroxy terpene, or terpene mixture, in the autoclave is terminated andthe autoclave is permitted to cool to a temperature of approximately 90C. and the contents of the autoclave are then discharged into a suitablereceptacle and permitted to cool to room temperature.

A suitable quantity of the above product, say from about .02% to about.2%, by weight, based on the weight of the viscose to which it is added,

is mixed with a suitable delusterant, such as a pigment like titaniumdioxide, or a mineral oil, in a colloid mill with sufficient water toform a finely divided dispersion, and the dispersion is then added to aviscose spinning solution and mixed therewith in a tank provided withmeans for agitation of the contents thereof.

After mixing, the viscose solution may be filtered or otherwise treatedby conventional means to remove foreign matter therefrom preparatory tospinning the viscose into suitable filaments or yarn. Rayon produced bythe above-described method is uniformly dull in appearance and has thedelusterant pigment or oil evenly distributed therein, thus providingrayon of uniform tensile strength.

The following specific examples. in which the parts are given by weight,will serve to illustrate and explain the present invention.

Example 1 parts of the reaction product produced by reacting 510 partsof alpha-terpineol with 1020 parts of ethylene oxide, in the presence ofan alkaline catalyst, at a temperature of 105 C. to 147 C.-, and at amaximum pressure of 120 pounds per square inch, during a period of aboutthree hours, is dispersed in 800 parts of white mineral oil having aSaybolt viscosity of to at F. by warming the materials together at atemperature of 60 C. The mixture is then stirred into a slurry of 1250parts of water and 400 parts of titanium dioxide. The entire mixture isthen milled in a colloid mill provided with recirculating means, at asetting of .0014 inch between the ro Qi and stator of the mill. 315parts of the 3 resulting mixture is added to 5000 parts of a viscosespinning solution and stirred for fifteen minutes with a laboratorystirrer. Observation of particle size may be made after the solution hasbeen permitted to stand overnight under a vacuum of 27 inches of mercuryand at a temperature of 16 C. Samples taken from the top of the solutionwhen examined microscopically. using an oil-immersion lens and 900magnifications are found to have the pigment and oil present therein ina finely divided and uniformly dispersed condition. In uniformity ofdispersion and particle size of delusterant, the viscose solutioncontaining my improved dispersing agents is found to be superior to aviscose solution containing the same delusterants, but in which one ofthe usual dispersing agents is employed.

Example 2 600 parts of terpenyl ethylene glycol ether and 600 parts oftechnical grade alpha-terpineol are admixed with 5 parts of solid sodiumhydroxide catalyst by triturating the materials. This mixture is placedin an autoclave which is heated to an initial reaction temperature of130 G. Then 700 parts of ethylene oxide are gradually introduced intothe autoclave during a period of about one hour, while agitating theautoclave, and during this period the temperature of the autoclave ispermitted to increase to 149 C. The reaction is controlled to permit amaximum pressure during the reaction of about 100 pounds per squareinch, and upon completion of the reaction, the pressure decreased tozero gauge. The reaction product is a straw-colored, fairly viscous oilyliquid. having a specific gravity of 1.011 at 25 C. and a refractiveindex of 1.4760- The product is easily dispersible in either refinedmineral oil having a Saybolt viscosity of 80 to 100, or in water, and itis soluble in alcohol.

One part of the above dispersing agent is stirred into parts of mineraloil having a Saybolt viscosity of about 85. Then 3000 parts of water areplaced in a tank provided with stirring means and 1.8 parts of titaniumdioxide are added to the water and mixed therewith by stirring. Then themineral oil containing the dispersing agent is poured into thewater-titanium dioxide mixture. The entire mixture is then passedthrough a colloid mill to further comminute the oil and titanium dioxideparticles and globules, respectively. The resulting dispersion is thenadded to a standard viscose mixer containing 2500 parts of viscosesolution and stirred therewith for a period of one hour. After mixing,the material is passed through a filter press and air is removedtherefrom by vacuum, employing the customary procedure. Particle sizemeasurements are then made using a microscope equipped with anoilimmersion lens and at 9'70 magnifications and showed an average oilglobule size of two microns and an average particle size of one micronfor the titanium dioxide particles.

The dispersing agent described above is particularly effective inemulsifying oil as well as dispersing titanium dioxide pigment.

' Example 3 910 parts of commercial pine oil consisting of a mixture ofterpene alcohols and terpene hydrocarbons is admixed with 5 parts ofsolid sodium hydroxide catalyst by triturating the materials. Thismixture is placed in an autoclave provided with heating'and agitatingmeans, and heated 4 to an initial reaction temperature of about 136 C.Then 970 parts of ethylene oxide are gradually introduced into theautoclave during a period of about one and a half hours, while agitatingthe autoclave, and during this period the temperature of the autoclaveis permitted to increase to a maximum of about 193 C. The reaction iscontrolled so that a maximum pressure of about pounds per square inch isattained during the reaction, and upon completion of the reaction, thepressure decreased to zero gauge. The reaction product is a soft, greasysolid, easily dispersible in either oil or water, and soluble inalcohol.

60 parts of the above-described dispersing agent is mixed with 800 partsof refined mineral oil by warming and stirring the materials together.This mixture is then added to a colloid mill containing 400 parts oftitanium dioxide and 1250 parts of water and milled together for aboutone minute with recirculation. 31.3 parts of the dispersion thus formedis stirred into 5000 parts of viscose solution with a laboratory stirrerfor about fifteen minutes. After mixing, the material is passed througha filter press and air is removed therefrom by vacuum, employing thecustomary procedure. The mixture is permitted to stand overnight andsamples are removed from the top and from themiddle of the container.Particle size measurements are then made using a microscope equippedwith an oil-immersion lens and at 970 magnifications and showed nodifference in uniformity of dispersion or in particle size between thesamples taken from the top and from the middle of the container. Themaximum size of the oil globules is two and a half microns and theaverage size is one and a fourth microns. The maximum size of titaniumdioxide particles is one and a half microns and the average size is .75micron. 4

In dispersing mixtures of delusterants for rayon such as titaniumdioxide, which is capable of being wetted more readily by hydrophilicthan by hydrophobic substances, and refined mineral oil which isextremely hydrophobic in character, it is advantageous in obtaining afinely divided dis- .persion of these delusterants to employ a mixtureof the dispersing agents made in accordance with my above-mentionedcopending application, said mixture consisting of approximately equalproportions by weight of the products made according to Examples 1 and 4of said application.

After viscose containing delusterants and my improved dispersing agentshas been spun in the usual manner into a coagulating bath, it iscustomary to wash it with hot water to remove acid and other coagulatingmaterial from the yarn. This washing operation also substantiallyentirely removes the dispersing agent but leaves the delusterant fixedin the yarn.

Dispersing agents utilized in the present invention, to be mosteffective for dispersing delusterants in viscose, should be produced bythe reaction of at least three moles of alkylene oxide per mole ofterpene compound. Preferably, however, from four to seven moles ofalkylene oxide per mole of terpene'compound are necessary to providemaximum water-dispersibility Of the final reaction product.

While the invention has been described in detail with specific examples,such examples are illustrative and are not given as limitations, sinceother modifications within the spirit and scope of the invention will beapparent to those skilled in the art. Hence, the invention is to beunderstood as limited only as indicated. in the appended claims, inwhich the intent is to set forth all the novelty over the prior art.

I claim:

1. As a spinning solution for use in the production of low lusterfilaments. a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product of one mole of a terpene selected from the groupconsisting of unsaturated and bydroxy terpenes reacted with at leastthree .moles of an alkylene oxide.

2. As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product of one mole of a mixture of unsaturated terpenes and atleast three moles of an alkylene oxide.

3. As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product of one mole of a hydroxy terpene reacted with at leastthree moles of an alkylene oxide.

4. As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent the reaction product formed by reacting at least threemoles of an alkylene oxide per mole of a terpene selected from the groupconsisting of unsaturated and hydroxy terpenes.

5. As aspinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent the reaction product formed by reacting at least threemoles of ethylene oxide per mole of a terpene selected from the groupconsisting of unsaturated and hydroxy terpenes.

6. As a spinning solutionfor use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent the reaction product formed by reacting at least threemoles of propylene oxide per mole of a terpene selected from the groupconsisting of unsaturated and hydroxy terpenes.

7. As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent the reaction product formed by the reaction of .onemole of a hydroxy terpene and at least three moles of ethylene oxide.

8. As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product formed by reacting one mole of alpha-terpineol and atleast three moles of ethylene oxide.

9. A a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight,

01' the reaction product formed by reacting one mole 01' a mixture ofhydroxy terpenes and at least three moles of an alkylene oxide.

10. As a spinning solution'for use in the production of low lusterfilaments, a viscose solution containing. a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product formed by reacting one mole of a mixture of terpenylethylene'glycol ether and alpha-terpineol with at least three moles 01'an alkylene oxide.

11. As a spinning solution for use in the proagent from about .02% toabout .2%, by weight, a

of the reaction product formed by reacting an unsaturated terpene withfrom three to seven moles of an alkylene oxide.

13 As a spinning solution for use in the production of low lusterfilaments, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product formed by reacting from three to seven moles of analkylene oxide per mole of a hydroxy terpene.

14. As a spinning solution for use in the production of low lusterfilament-s, a viscose solution containing a delusterant and as adispersing agent from about .02% to about .2%, by weight, of thereaction product formed by reacting from three to seven moles of analkylene oxide with a mole of a mixture of hydroxy terpenes.

l5.A process for the production of viscose rayon of diminished lusterwhich comprises incorporating in a viscose spinning solution, adelusterant and as a dispersing agent from about .02% to about .2%, byweight, of a reaction product formed by reacting one mole of a terpeneselected from the group consisting of unsaturated and hydroxy terpenes.with at least three moles of an alkylene oxide.

16. A process for the production of viscose rayon ofdiminished lusterwhich comprises incorporating in a viscose spinning solution, adelusterant and as a dispersing agent from about ,02% to about .2%, byweight, of a reaction product formed by reacting one mole of a mixtureof unsaturated terpenes with at least three moles of an alkylene oxide.

17. A process for the production of viscose rayon of diminished lusterwhich comprises incorporating in a viscose spinning solution, an aqueousdispersion comprising a delusterant and as a dispersing agent from about.02% to about .2%, by weight, based on the final spinning solution, 01 areaction product formed by reacting an unsaturated terpene with analkylene oxide in the proportion of at least three moles of alkyleneoxide per mole of the ter ne.

18. A process for the production of viscose rayon of diminished lusterwhich comprises incorporating in a viscose spinning solution, an aqueousdispersion comprising a delusterant and from about .02% to about .2%, byweight based on the final spinning solution, of a reaction productformed by reacting one mole of a hydroxy terpene with at least threemoles of an alkylene oxide.

WILLIAM O. ISRAEL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,053,708 Fife Sept. 8, 19362,136,011 Humphrey Nov. 8, 1938 2,220,462 Sheflield Nov, 5, 19402,227,495 Gloor Jan. 7, 1941 2,347,337 Sheflleld Apr. 25, 1944Certificate of Correction Patent No. 2,440,094. April 20, 1948.

WILLIAM O. ISRAEL .It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows? Column 5, line 60, claim 9, for A a. read As a; column 6,line 41, claim 16, for ,02% read 02%; line 58, claim 18, after the wordand insert as a dispersing agent; and that the said Letters Patentshould be read with these corrections therein that the same may conformto the record of the case in the Patent Office.

Signed and sealed this 6th day of July, A; D. 1948.

THOMAS F. MURPHY,

Assistant Commissioner of. Patents.

